WO2023274796A1 - Three-chamber electrolytic cell for the production of alkali metal alkoxides - Google Patents
Three-chamber electrolytic cell for the production of alkali metal alkoxides Download PDFInfo
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- WO2023274796A1 WO2023274796A1 PCT/EP2022/066943 EP2022066943W WO2023274796A1 WO 2023274796 A1 WO2023274796 A1 WO 2023274796A1 EP 2022066943 W EP2022066943 W EP 2022066943W WO 2023274796 A1 WO2023274796 A1 WO 2023274796A1
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- WIPO (PCT)
- Prior art keywords
- chamber
- electrolytic cell
- solution
- internals
- cation
- Prior art date
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- -1 alkali metal alkoxides Chemical class 0.000 title claims abstract description 29
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000009792 diffusion process Methods 0.000 claims abstract description 45
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 45
- 230000004888 barrier function Effects 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 11
- 150000004820 halides Chemical class 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 26
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 239000008151 electrolyte solution Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 17
- 235000002639 sodium chloride Nutrition 0.000 description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- 239000010936 titanium Substances 0.000 description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 230000005484 gravity Effects 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 241000047703 Nonion Species 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 238000010327 methods by industry Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229920003934 Aciplex® Polymers 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
- C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/13—Single electrolytic cells with circulation of an electrolyte
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
Definitions
- the present invention relates to an electrolytic cell which has three chambers, the middle chamber being separated from the cathode chamber by a solid electrolyte which is permeable to cations, for example NaSICON, and from the anode chamber by a diffusion barrier.
- the invention is characterized in that the middle chamber comprises internals.
- the electrolytic cell according to the invention solves the problem that a concentration gradient forms in the middle chamber of the electrolytic cell during electrolysis, which leads to locally reduced pH values and thus to damage to the solid electrolyte.
- the internals cause the electrolyte solution to be swirled as it flows through the central chamber during the electrolysis, which prevents the formation of a pH gradient.
- the present invention relates to a method for producing an alkali metal alkoxide solution in the electrolytic cell according to the invention.
- the electrochemical production of alkali metal alkoxide solutions is an important industrial process which is described, for example, in DE 10360758 A1, US 2006/0226022 A1 and WO 2005/059205 A1.
- the principle of this process is reflected in an electrolytic cell, in the anode chamber of which there is a solution of an alkali salt, for example common salt or NaOH, and in the cathode chamber of which the alcohol in question or a low-concentration alcoholic solution of the alkali metal alcoholate in question, for example sodium methoxide or sodium ethoxide, is located.
- the cathode compartment and the anode compartment are separated by a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
- a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
- chlorine is formed at the anode - if a chloride salt of the alkali metal is used - and hydrogen and alcohol ions are formed at the cathode.
- the charge is equalized by the alkali metal ions migrating from the middle chamber into the cathode chamber via the ceramic that is selective for them.
- the charge equalization between the middle chamber and the anode chamber takes place through the migration of cations when using cation exchange membranes or the migration of anions when using anion exchange membranes or through the migration of both types of ions when using non-specific diffusion barriers.
- WO 2014/008410 A1 describes an electrolytic process for the production of elemental titanium or rare earths. This process is based on the fact that titanium chloride is formed from TiO2 and the corresponding acid, this reacts with sodium alcoholate to form titanium alcoholate and NaCl and is finally electrolytically converted to elementary titanium and sodium alcoholate.
- WO 2007/082092 A2 and WO 2009/059315 A1 describe processes for the production of biodiesel in which triglycerides are first converted into the corresponding alkali metal triglycerides with the aid of alcoholates electrolytically produced via NaSICON and in a second step with electrolytically produced protons to form glycerol and the respective alkali metal hydroxide be implemented. Accordingly, methods are described in the prior art which are carried out in electrolytic cells with an ion-permeable layer, such as, for example, NaSiCON solid electrolytes. However, these solid electrolytes typically have the disadvantage that they are not long-term stable to aqueous acids.
- the cathode chamber and the middle chamber of the cell are separated by a cation-permeable solid electrolyte such as NaSICON.
- the middle chamber is supplied with solution from the cathode chamber, for example.
- US 2010/0044242 A1 also describes in Figure 6 that solution from the middle chamber can be mixed with solution from the anode chamber outside the chamber in order to obtain sodium hypochlorite.
- Such cells have also been proposed in the prior art for the production or purification of alkali metal alkoxides.
- 5,389,211 A describes a process for purifying alkoxide solutions in which a three-chamber cell is used, in which the chambers are separated from one another by cation-selective solid electrolytes or non-ionic partitions. The middle chamber is used as a buffer chamber to prevent the cleaned Alkoxide or hydroxide solution from the cathode compartment mixes with the contaminated solution from the anode compartment.
- DE 4233191 A1 describes the electrolytic production of alkoxides from salts and alkoxides in multi-chamber cells and stacks of several cells.
- WO 2008/076327 A1 describes a process for preparing alkali metal alkoxides.
- a three-chamber cell is used, the middle chamber of which is filled with alkali metal alkoxide (see, for example, paragraphs [0008] and [0067] of WO 2008/076327 A1).
- WO 2009/073062 A1 A similar arrangement is described in WO 2009/073062 A1. However, this arrangement has the disadvantage that the alkali metal alkoxide solution is the desired product, but this is consumed as a buffer solution and is continuously contaminated.
- the drop in pH is particularly critical in the middle chamber, as this is bounded by the ion-conducting ceramic. Gases are usually formed at the anode and the cathode, so that there is at least a certain degree of mixing in these chambers. On the other hand, such mixing does not take place in the middle chamber, so that the pH gradient develops in it. This undesirable effect is amplified by the fact that the brine is generally pumped relatively slowly through the electrolytic cell.
- the object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide and an electrolysis chamber which is particularly suitable for such a process.
- the electrolytic cell E ⁇ 100> comprises at least one anode chamber K A ⁇ 101>, at least one cathode chamber K K ⁇ 102> and at least one intermediate chamber K M ⁇ 103>, where K A ⁇ 101> is an anodic Electrode E A ⁇ 104> and an outlet A KA ⁇ 106>, where K K ⁇ 102> comprises a cathodic electrode EK ⁇ 105>, an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>, where K M ⁇ 103> comprises an inlet Z KM ⁇ 108>, is separated from K A ⁇ 101> by a diffusion barrier D ⁇ 110> and is separated from K K ⁇ 102> by an alkali cation-conducting solid electrolyte F K ⁇ 111>, where K M ⁇ 103> and K A ⁇ 101> are connected to each other by a connection V AM ⁇ 112>, through which liquid can be conducted from K M ⁇ 103> to K A ⁇ 101
- the present invention relates to a method for producing a solution L 1 ⁇ 115> of an alkali metal alcoholate XOR in the alcohol ROH in an electrolytic cell E ⁇ 100> according to the first aspect of the invention, the method comprising the following steps (a ), (b) and (c) comprises: (a) a solution L 2 ⁇ 113> comprising the alcohol ROH is passed through K K ⁇ 102>, (b) a neutral or alkaline aqueous solution L 3 ⁇ 114> of a Salt S comprising X as cation is passed through K M , then through V AM , then through K A ⁇ 101>, (c) voltage is applied between E A ⁇ 104> and E K ⁇ 105>, resulting in A KK ⁇ 109> the solution L 1 ⁇ 115> is obtained, the concentration of XOR in L 1 ⁇ 115> being higher than that in L 2 ⁇ 113>, and whereby at the outlet A KA ⁇ 106> an aqueous solution L 4 ⁇
- FIG. 1 shows a preferred embodiment of an electrolytic cell ⁇ 100> according to the invention and of the method according to the invention.
- the three-chamber cell E ⁇ 100> comprises a cathode chamber K K ⁇ 102>, an anode chamber K A ⁇ 101> and a middle chamber K M ⁇ 103> lying between them.
- the cathode chamber K K ⁇ 102> comprises a cathodic electrode EK ⁇ 105>, an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>.
- Anode chamber K A ⁇ 101> comprises an anodic electrode E A ⁇ 104> and drain A KA ⁇ 106> and is connected to middle chamber K M ⁇ 103> via connection V AM ⁇ 112>.
- the middle chamber K M ⁇ 103> includes an inlet Z KM ⁇ 108>.
- the three chambers are delimited by an outer wall ⁇ 117> of the three-chamber cell E ⁇ 100>.
- the cathode chamber K K ⁇ 102> is also separated from the middle chamber K M ⁇ 103> by a NaSICON solid electrolyte F K ⁇ 111> that is selectively permeable for sodium ions.
- the middle chamber K M ⁇ 103> is additionally in turn separated from the anode chamber K A ⁇ 101> by a diffusion barrier D ⁇ 110>.
- the NaSICON solid electrolyte F K ⁇ 111> and the diffusion barrier D ⁇ 110> extend over the entire depth and height of the three-chamber cell E ⁇ 100>.
- the diffusion barrier D ⁇ 110> is made of glass.
- the connection V AM ⁇ 112> is formed outside the electrolytic cell E ⁇ 100>, in particular by a tube or hose, the material of which can be selected from rubber, metal or plastic.
- liquid can be conducted from the central chamber K M ⁇ 103> into the anode chamber K A ⁇ 101> outside the outer wall WA ⁇ 117> of the three-chamber cell E ⁇ 100>.
- connection V AM ⁇ 112> connects an outlet A KM ⁇ 118>, which breaks through the outer wall WA ⁇ 117> of the electrolytic cell E ⁇ 100> at the bottom of the central chamber K M ⁇ 103>, with an inlet Z KA ⁇ 119>, which breaks through the outer wall W A ⁇ 117> of the electrolytic cell E ⁇ 100> at the bottom of the anode chamber K A ⁇ 101>.
- An aqueous solution of sodium chloride L 3 ⁇ 114> with a pH of 10.5 is added via the inlet Z KM ⁇ 108> in the same direction as gravity into the middle chamber KM ⁇ 103>.
- connection V AM ⁇ 112> which is formed between an outlet A KM ⁇ 118> of the middle chamber K M ⁇ 103> and an inlet Z KA ⁇ 119> of the anode chamber KA ⁇ 101>, forms the middle chamber K M ⁇ 103 > connected to the anode chamber K A ⁇ 101>.
- Sodium chloride solution L 3 ⁇ 114> is conducted through this connection V AM ⁇ 112> from the middle chamber KM ⁇ 103> into the anode chamber KA ⁇ 101>.
- a solution of sodium methoxide in methanol L2 ⁇ 113> is fed into the cathode chamber K K ⁇ 102> via the inlet Z KK ⁇ 107>.
- a voltage is applied between the cathodic electrode E K ⁇ 105> and the anodic electrode EA ⁇ 104>.
- methanol im Electrolyte L2 ⁇ 113> reduced to methoxide and H2 (CH 3 OH + e- ⁇ CH 3 O- + 1 ⁇ 2 H2).
- Sodium ions diffuse from the middle chamber K M ⁇ 103> through the NaSICON solid electrolyte F K ⁇ 111> into the cathode chamber K K ⁇ 102>.
- Chlorine gas Cl2 forms hypochlorous acid and hydrochloric acid in water according to the reaction Cl2 + H2O ⁇ HOCl + HCl, which react acidically with other water molecules.
- the acidity damages the NaSICON solid electrolyte ⁇ 111>, but is limited by the arrangement according to the invention in the anode chamber K A ⁇ 101> and is thus kept away from the NaSICON solid electrolyte F K ⁇ 111> in the electrolytic cell E ⁇ 100>. This increases its lifespan considerably.
- the middle chamber K M ⁇ 103> there are also fixtures ⁇ 120> in the form of a net-like wire basket ⁇ 122> which contains glass or plastic balls ⁇ 121>.
- the wire basket ⁇ 122> is placed loosely in the middle chamber ⁇ 103 >, but can also be attached to the inside of the outer wall of ⁇ 117>.
- the aqueous solution L 3 ⁇ 114> fed in through the inlet Z KM ⁇ 108> is guided through these internals ⁇ 120>, as a result of which turbulence and turbulence occur.
- These turbulences in the solution L 3 ⁇ 114> prevent a pH gradient building up in the central chamber K M ⁇ 103> as the electrolysis progresses and thus prevent the formation of a low pH value in the area immediately adjacent to the NaSICON solid electrolyte ⁇ 111> Solution. This further increases the durability of the NaSICON solid electrolyte ⁇ 111>.
- connection V AM ⁇ 112> from the central chamber K M ⁇ 103> to the anode chamber K A ⁇ 101> is formed by a perforation in the diffusion barrier D ⁇ 110>.
- wire basket ⁇ 122> loosely located in the middle chamber K M ⁇ 103> several pins made of glass or plastic ⁇ 123-2> are attached to the NaSICON solid electrolyte FK ⁇ 111> as internals ⁇ 120>, which can be inserted into the middle chamber K M ⁇ 103> protrude.
- Electrolytic cell E The first aspect of the invention relates to an electrolytic cell E ⁇ 100>.
- the electrolytic cell E ⁇ 100> comprises at least one anode chamber KA ⁇ 101>, at least one cathode chamber KK ⁇ 102> and at least one intermediate chamber KM ⁇ 103>.
- This also includes electrolytic cells E ⁇ 100>, which have more than one anode chamber KA ⁇ 101> and/or cathode chamber KK ⁇ 102> and/or middle chamber KM ⁇ 103>.
- electrolytic cells in which these chambers are joined together in a modular manner, are described, for example, in DD 258143 A3 and US 2006/0226022 A1.
- the anode chamber K A ⁇ 101> includes an anodic electrode E A ⁇ 104>.
- anodic electrode E A ⁇ 104> Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the second aspect of the invention can be used as such an anodic electrode E A ⁇ 104>. Such are described in particular in WO 2014/008410 A1, paragraph [024] or DE 10360758 A1, paragraph [031].
- This electrode E A ⁇ 104> can consist of one layer or of several planar layers parallel to one another, each of which can be perforated or expanded.
- the anodic electrode E A ⁇ 104> comprises in particular a material selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, nickel titanate, noble metals such as platinum in particular, which is deposited on a carrier such as titanium or Kovar ® (an iron /nickel/cobalt alloy, in which the individual proportions are preferably as follows: 54% by mass iron, 29% by mass nickel, 17% by mass cobalt).
- Other possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide, titanium diboride.
- the anodic electrode E A ⁇ 104> preferably comprises a titanium anode (RuO2+IrO2/Ti) coated with ruthenium oxide/iridium oxide.
- the cathode chamber K K ⁇ 102> includes a cathodic electrode E K ⁇ 105>. Any electrode familiar to a person skilled in the art that is stable under the conditions can be used as such a cathodic electrode E K ⁇ 105>. Such are described in particular in WO 2014/008410 A1, paragraph [025] or DE 10360758 A1, paragraph [030].
- This electrode EK ⁇ 105> can be selected from the group consisting of mesh wool, three-dimensional matrix structure or "spheres".
- the cathodic electrode E K ⁇ 105> comprises in particular a material selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium supported on carbon, titanium.
- EK ⁇ 105> preferably comprises nickel.
- the at least one middle chamber K M ⁇ 103> is located between the anode chamber K A ⁇ 101> and the cathode chamber K K ⁇ 102>.
- the electrolytic cell E ⁇ 100> usually has an outer wall W A ⁇ 117>.
- the outer wall W A ⁇ 117> is in particular made of a material which is selected from the group consisting of steel, preferably rubberized steel, plastic, which is in particular made of Telene ® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride) is selected.
- W A ⁇ 117> can be perforated in particular for inlets and outlets.
- the at least one anode chamber K A ⁇ 101>, the at least one cathode chamber K K ⁇ 102> and the at least one intermediate chamber K M ⁇ 103> are then located within W A ⁇ 117>.
- K M ⁇ 103> is separated from K A ⁇ 101> by a diffusion barrier D ⁇ 110> and separated from K K ⁇ 102> by an alkali cation-conducting solid electrolyte F K ⁇ 111>.
- Any material which is stable under the conditions of the method according to the second aspect of the invention and which prevents the transfer of protons from the liquid in the anode chamber K A ⁇ 101> into the middle chamber K M can be used for the diffusion barrier D ⁇ 110> ⁇ 103> prevented or slowed down.
- a non-ion-specific dividing wall or a membrane permeable to specific ions is used as the diffusion barrier D ⁇ 110>.
- the diffusion barrier D ⁇ 110> is preferably a non-ion-specific partition.
- the material of the non-ion-specific partition wall is in particular selected from the group consisting of fabric, in particular textile fabric or metal fabric, glass, in particular sintered glass or glass frits, ceramic, in particular ceramic frits, membrane diaphragms, and is selected particularly preferably glass.
- the diffusion barrier D ⁇ 110> is a “membrane permeable to specific ions”, this means according to the invention that the respective membrane favors the diffusion of certain ions through it compared to other ions.
- membranes are meant that favor the diffusion through them of ions of a certain type of charge compared to oppositely charged ions. More preferably, specific ion permeable membranes also favor the diffusion of certain ions having one charge type through them over other ions of the same charge type.
- the diffusion barrier D ⁇ 110> is a “membrane permeable to specific ions”
- the diffusion barrier D ⁇ 110> is in particular an anion-conducting membrane or a cation-conducting membrane.
- anion-conducting membranes are those which selectively conduct anions, preferably selectively specific anions. In other words, they favor the diffusion of anions through them over that of cations, especially protons, more preferably they additionally favor the diffusion of certain anions through them over the diffusion of other anions through them.
- cation-conducting membranes are those which selectively conduct cations, preferably selectively specific cations.
- “Favour the diffusion of certain ions X compared to the diffusion of other ions Y” means in particular that the diffusion coefficient (unit m 2 /s) of the ion species X at a given temperature for the membrane in question is higher by a factor of 10, preferably 100, preferably 1000 as the diffusion coefficient of the ionic species Y for the membrane in question.
- the diffusion barrier D ⁇ 110> is a "membrane that is permeable to specific ions" it is preferably an anion-conducting membrane, because this is particularly good at preventing the diffusion of protons from the anode chamber KA ⁇ 101> into the middle chamber KM ⁇ 103>.
- a membrane which is selective for the anions comprised by the salt S is used as the anion-conducting membrane.
- the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
- Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
- a membrane selective for halides, more preferably chloride, is preferably used as the anion-conducting membrane.
- Anion-conducting membranes are, for example, by MA Hickner, AM Herring, EB Coughlin, Journal of Polymer Science, Part B: Polymer Physics 2013, 51, 1727-1735, by CG Arges, V. Ramani, PN Pintauro, Electrochemical Society Interface 2010, 19, 31-35, in WO 2007/048712 A2 and on page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003).
- the diffusion barrier D ⁇ 110> is a cation-conducting membrane, it is in particular a membrane that is selective for the cations comprised by the salt S. Even more preferably, the diffusion barrier D ⁇ 110> is an alkali cation-conducting membrane, even more preferably a potassium and/or sodium ion-conducting membrane, most preferably a sodium ion-conducting membrane.
- Cation-conducting membranes are described, for example, on page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003). Accordingly, organic polymers, which are selected in particular from polyethylene, polybenzimidazoles, polyetherketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, polyperfluoroethylene, are even more preferably used as the cation-conducting membrane, with these covalently bonded functional groups selected from -SO 3 - , -COO-, -PO 3 2- , -PO 2 H-, preferably -SO 3 -, (described in DE 102010062804 A1, US Pat.
- Neosepta® membranes are described, for example, by SA Mareev, D.Yu.
- a cation-conducting membrane is used as the diffusion barrier D ⁇ 110>, this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula PNAFION, where n and m are independently an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 , more preferably an integer from 10 2 to 10 4 .
- any solid electrolyte which can transport cations, in particular alkali cations, more preferably sodium cations, from the central chamber K M ⁇ 103> into the cathode chamber K K ⁇ 102> can be used as the alkali cation-conducting solid electrolyte F K ⁇ 111>.
- Such solid electrolytes are known to the person skilled in the art and are known, for example, in DE 102015013155 A1, in WO 2012/048032 A2, paragraphs [0035], [0039], [0040], in US 2010/0044242 A1, paragraphs [0040], [0041 ], in DE 10360758 A1, paragraphs [014] to [025].
- NaSICON preferably has a structure of the formula M I 1+2w+x-y+z M II w M III x Zr IV 2-wxy M V y (SiO 4 )z (PO 4 )3-z.
- M I is selected from Na + , Li + , preferably Na + .
- M II is a divalent metal cation preferably selected from Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 2+ , Ni 2+ , more preferably selected from Co 2+ , Ni 2+ .
- M III is a trivalent metal cation, preferably selected from Al 3+ , Ga 3+ , Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , Lu 3+ , Fe 3+ , Cr 3+ , more preferably selected from Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , particularly preferably selected from Sc 3+ , Y 3+ , La 3+ .
- M V is a pentavalent metal cation, preferably selected from V 5+ , Nb 5+ , Ta 5+ .
- the Roman indices I, II, III, IV, V indicate the oxidation numbers in which the respective metal cations are present.
- NaSICON more preferably has a structure of the formula Na(1 + v)Zr2SivP(3-v)O12, where v is a real number such that 0 ⁇ v ⁇ 3.
- the cathode chamber K K ⁇ 102> also comprises an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>, which allows liquid, such as the solution L 2 ⁇ 113>, to flow into the cathode chamber K K ⁇ 102>. to add and liquid contained therein, such as the solution L 1 ⁇ 115> to remove.
- the inlet Z KK ⁇ 107> and the outlet A KK ⁇ 109> are attached to the cathode chamber K K ⁇ 102> in such a way that the liquid makes contact with the cathodic electrode E K ⁇ 105> as it flows through the cathode chamber K K ⁇ 102>.
- the anode chamber K A ⁇ 101> also includes an outlet A KA ⁇ 106>, which makes it possible to remove liquid located in the anode chamber K A ⁇ 101>, for example the aqueous solution L 4 ⁇ 116>.
- the middle chamber K M ⁇ 103> includes an inlet Z KM ⁇ 108>, while K A ⁇ 101> and K M ⁇ 103> are connected to one another by a connection V AM ⁇ 112>, through which liquid from K M ⁇ 103> can be directed into K A ⁇ 101>.
- a solution L 3 ⁇ 114> can be added to K M ⁇ 103> via the inlet Z KM ⁇ 108> and this can be conducted through K M ⁇ 103>, then via V AM ⁇ 112> into the anode chamber KA ⁇ 101> , and finally through the anode chamber K A ⁇ 101>.
- V AM ⁇ 112> and the drain A KA ⁇ 106> are attached to the anode chamber K A ⁇ 101> in such a way that the solution L 3 ⁇ 114> when flowing through the anode chamber K A ⁇ 101> touches the anodic electrode EA ⁇ 104> contacted.
- This is the prerequisite for the aqueous solution L 4 ⁇ 116> being obtained when the method according to the invention is carried out according to the second aspect of the invention at the outflow A KA ⁇ 106> if the solution L 3 ⁇ 114> is first divided by K M ⁇ 103>, then V AM ⁇ 112>, then K A ⁇ 101>.
- connection V AM ⁇ 112> can be formed inside the electrolytic cell E ⁇ 100> and/or outside, preferably inside, the electrolytic cell E ⁇ 100>. If the connection V AM ⁇ 112> is formed within the electrolytic cell E ⁇ 100>, it is preferably formed by at least one perforation in the diffusion barrier D ⁇ 110>.
- connection V AM ⁇ 112> is formed outside of the electrolytic cell E ⁇ 100>, it is preferably formed by a connection of K M ⁇ 103> and K A ⁇ 101> running outside of the electrolytic cell E ⁇ 100>, in particular by the fact that in the middle chamber K M ⁇ 103> an outlet A KM ⁇ 118> through the outer wall W A ⁇ 117>, preferably at the bottom of the middle chamber K M ⁇ 103>, with the inlet Z KM ⁇ 108> even more preferably at the top of the middle chamber K M ⁇ 103> is formed, and in the anode chamber K A ⁇ 101> an inlet Z KA ⁇ 119> through the outer wall W A ⁇ 117>, preferably at the bottom of the anode chamber K A ⁇ 101>, and these are connected by a line, for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic.
- a line for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic
- the drain A KA ⁇ 106> is then even more preferably at the top of the anode chamber KA ⁇ 101>.
- "Outflow A KM ⁇ 118> at the bottom of the middle chamber K M ⁇ 103>” means that the outflow A KM ⁇ 118> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> fills the middle chamber K M ⁇ 103> leaves in the same direction as gravity.
- Inlet Z KA ⁇ 119> at the bottom of the anode chamber K A ⁇ 101> means that the inlet Z KA ⁇ 119> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> flows into the anode chamber K A ⁇ 101> occurs against gravity.
- Inlet Z KM ⁇ 108> at the top of the middle chamber K M ⁇ 103> means that the inlet Z KM ⁇ 108> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> enters the middle chamber K M ⁇ 103> in the same direction as gravity.
- Outflow A KA ⁇ 106> at the top of the anode chamber K A ⁇ 101> means that the outflow A KA ⁇ 106> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 4 ⁇ 116> fills the anode chamber K A ⁇ 101> leaves against gravity.
- This embodiment is particularly advantageous and therefore preferred if the outlet A KM ⁇ 118> through the outer wall WA ⁇ 117> at the bottom of the middle chamber KM ⁇ 103>, and the inlet Z KA ⁇ 119> through the outer wall WA ⁇ 117> at the bottom of the anode chamber K A ⁇ 101>.
- This arrangement makes it particularly easy to discharge gases with L 4 ⁇ 116> formed in the anode chamber K A from the anode chamber K A ⁇ 101> in order to then separate them further.
- Z KM ⁇ 108> and A KM ⁇ 118> are arranged on opposite sides of the outer wall W A ⁇ 117> of the central chamber K M ⁇ 103> ( eg Z KM ⁇ 108> at the bottom and A KM ⁇ 118> at the top of the electrolytic cell E ⁇ 100> or vice versa) and Z KA ⁇ 119> and A KA ⁇ 106> on opposite sides of the outer wall W A ⁇ 117> of the Anode chamber K A ⁇ 101> arranged (i.e.
- Z KA ⁇ 119> at the bottom and A KA ⁇ 106> at the top of the electrolytic cell E ⁇ 100> or vice versa as shown in particular in Figure 1.
- L 3 ⁇ 114> must flow through the two chambers KM ⁇ 103> and KA ⁇ 101> through this geometry.
- Z KA ⁇ 119> and Z KM ⁇ 108> can be formed on the same side of the electrolytic cell E ⁇ 100>, with A KM ⁇ 118> and A KA ⁇ 106> then automatically also being formed on the same side of the electrolytic cell E ⁇ 100> are.
- Z KA ⁇ 119> and Z KM ⁇ 108> may be formed on opposite sides of the electrolytic cell E ⁇ 100>, in which case A KM ⁇ 118> and A KA ⁇ 106> are automatically also formed on opposite sides of the electrolytic cell E ⁇ 100>.
- connection V AM ⁇ 112> is formed within the electrolytic cell E ⁇ 100>, this can be ensured in that one side ("side A") of the electrolytic cell E ⁇ 100>, which is the top or the
- the bottom of the electrolytic cell E ⁇ 100> is preferably the top, as shown in Figure 2, includes the inlet Z KM ⁇ 108> and the outlet A KA ⁇ 106> and the diffusion barrier D ⁇ 110> starting from this side ("side A”) extends into the E ⁇ 100> electrolytic cell, but not all the way to the opposite side (“side B”) of the E ⁇ 100> electrolytic cell from side A, which is then the bottom or top of the Electrolytic cell E ⁇ 100> is sufficient and 50% or more of the height of the three-chamber cell E ⁇ 100>, more preferably 60% to 99% of the height of the three-chamber cell E ⁇ 100>, even more preferably 70% to 95% of the height of the three-chamber cell E ⁇ 100>, more preferably 80% to 90% of the height of the
- bottom of the electrolytic cell E ⁇ 100> is the side of the electrolytic cell E ⁇ 100> through which a solution (e.g. L 3 ⁇ 114> at A KM ⁇ 118> in Figure 1) exits the electrolytic cell E in the same direction as gravity or the side of the electrolytic cell E through which a solution (e.g. L2 ⁇ 113> at Z KK ⁇ 107> in Figures 1 and 2 and L 3 ⁇ 114> at A KA ⁇ 119> in Figure 1) of the electrolytic cell E against the Gravity is supplied.
- “top side of the electrolytic cell E” is the side of the electrolytic cell E through which a solution (e.g.
- the central chamber K M includes built-in components ⁇ 120>.
- internals ⁇ 120> are in the solid state of aggregation. Any objects or structures known to those skilled in the art that are sufficiently inert to the electrolysis conditions are suitable as such internals.
- the internals ⁇ 120> include, in particular, at least one material selected from rubber; Plastic chosen in particular from polystyrene, polypropylene, PVC, PVC-C; Glass; Porcelain; Metal.
- the metal is in particular a metal or an alloy of several metals selected from titanium, iron, molybdenum, chromium, nickel, preferably an alloy comprising at least two metals selected from titanium, iron, molybdenum, chromium, nickel, even more preferably a steel alloy comprising, in addition to iron, at least one other metal selected from titanium, molybdenum, chromium, nickel, and most preferably it is stainless steel.
- the internals ⁇ 120> are selected in particular from structured packings, unstructured packings (filling bodies) and trays, for example bubble-cap trays, valve trays, tunnel trays, Thormann trays, Phillips bell-bottom trays or sieve trays.
- Unstructured packings are generally random packings. Raschig rings, Pall rings, Berl saddles or Intalox® saddles are usually used as packing. Structured packings are sold, for example, under the trade name Mellapack® from Sulzer.
- the internals ⁇ 120> can be loose in the central chamber K M ⁇ 103>, for example balls ⁇ 121>, for example made of glass, in a basket made of wire frame ⁇ 122>, as shown in Figure 1.
- the internals ⁇ 120> can also be attached, for example to the solid electrolyte F K ⁇ 111>, to the diffusion barrier D ⁇ 110> or to the outer wall ⁇ 117> delimiting the inside of the central chamber K M ⁇ 103>.
- the attachment can be done by methods known to those skilled in the art, for example by screwing, clamping, gluing (plastic adhesive, PVC adhesive).
- the pins ⁇ 123-2> shown in Figure 2 are attached to the solid electrolyte FK ⁇ 111>, and the pins ⁇ 123-1> to the diffusion barrier D ⁇ 110>.
- Corresponding pegs can also be attached to the outer wall ⁇ 117> delimiting the inside of the central chamber K M ⁇ 103>, and then form stalactite or stalactite-like structures in the central chamber.
- the fixtures ⁇ 120> can be attached to the alkali cation-conducting solid electrolyte FK ⁇ 111> or to the diffusion barrier D ⁇ 110>, for example by being attached to a wire frame on the relevant wall.
- the internals ⁇ 120> make up a proportion ⁇ of 1 to 99%, more preferably 10 to 99%, even more preferably 40 to 90%, even more preferably 50 to 90% , more preferably 60 to 90%, most preferably 80 to 90% of the volume comprised by the central chamber K M .
- VO is the maximum volume of liquid, for example the electrolyte L 3 ⁇ 114>, which the central chamber K M ⁇ 103> can hold if it does not include any internals ⁇ 120>.
- V M is the maximum volume of liquid, for example the electrolyte L 3 ⁇ 114>, which the middle chamber K M ⁇ 103> can hold if it includes internals ⁇ 120>. It was surprisingly found that the internals ⁇ 120> in the central chamber K M ⁇ 103> lead to turbulence and turbulence in the electrolyte L 3 ⁇ 114> flowing through the central chamber K M ⁇ 103> during the method according to the invention. This slows down or completely prevents the build-up of a pH gradient during the electrolysis, which protects the acid-sensitive solid electrolyte FK ⁇ 111> and thus enables the electrolysis to run longer or prolongs the life of the electrolysis cell.
- the internals ⁇ 120> are fitted in the middle chamber K M ⁇ 103> in such a way that they prevent the flow of the electrolyte L 3 ⁇ 114> through the middle chamber K M ⁇ 103> and the anode chamber K A ⁇ 101 > enable to a sufficient extent or not completely block.
- the internals ⁇ 120> interrupt the direct path in the middle chamber K M between inlet Z KM ⁇ 108> and connection V AM ⁇ 112>.
- the following "thread test" is used to determine whether the direct route between inlet Z KM ⁇ 108> and connection V AM ⁇ 112> in the middle chamber KM is interrupted: 1.
- a thread is fed through the opening through which inlet Z KM ⁇ 108> opens into the middle chamber K M , and guided out of the opening through which the connection V AM ⁇ 112> opens into the middle chamber K M.
- the thread is so long that its ends lie outside the central chamber K M .
- a force is applied in the opposite direction to the respective end of the thread so that the thread tightens without breaking. 3. If there is at least one thread that touches the internals when it is introduced into the middle chamber and tightened according to steps 1. and 2., then the feature is that the direct path between inlet Z KM ⁇ 108> and connection V AM ⁇ 112> in the middle chamber K M is interrupted. 4. If no thread touches the internals when it is introduced into the middle chamber and tightened according to steps 1.
- the thread is selected in particular from sewing thread (eg from the Schrmann company), fishing line, twine.
- the method according to the second aspect of the invention comprises the following steps (a), (b) and (c) occurring simultaneously.
- step (a) a solution L 2 ⁇ 113> comprising the alcohol ROH, preferably comprising an alkali metal alkoxide XOR and alcohol ROH, is passed through K K ⁇ 102>.
- X is an alkali metal cation and R is an alkyl group of 1 to 4 carbon atoms.
- X is selected from the group consisting of Li + , K + , Na + , more preferably from the group consisting of K + , Na + .
- Most X Na + .
- R is preferably selected from the group consisting of n-propyl, iso-propyl, ethyl, methyl, more preferably selected from the group consisting of ethyl, methyl. Most preferably R is methyl.
- the solution L2 ⁇ 113> is preferably free of water. "Free of water” means according to the invention that the weight of the water in the solution L 2 ⁇ 113> based on the weight of the alcohol ROH in the solution L 2 ⁇ 113> (mass ratio) ⁇ 1:10, more preferably ⁇ 1:20, more preferably ⁇ 1:100, even more preferably ⁇ 0.5:100.
- the mass fraction of XOR in the solution L 2 ⁇ 113> is in particular >0 to 30% by weight, preferably 5 to 20% by weight, more preferably at 10 to 20% by weight, even more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
- the solution L 2 ⁇ 113> comprises XOR
- the mass ratio of XOR to alcohol ROH is still in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20 more preferably in the range 1:12 to 1:8, even more preferably at 1:10.
- a neutral or alkaline aqueous solution L 3 ⁇ 114> of a salt S comprising X as a cation is substituted by K M ⁇ 103>, then passed through V AM ⁇ 112>, then through K A ⁇ 101>.
- the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
- Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
- the pH of the aqueous solution L 3 ⁇ 114> is ⁇ 7.0, preferably in the range from 7 to 12, more preferably in the range from 8 to 11, even more preferably from 10 to 11, most preferably at 10.5.
- the mass fraction of the salt S in the solution L 3 ⁇ 113> is preferably in the range >0 to 20% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 10 to 20% by weight, most preferably at 20% by weight, based on the total solution L 3 ⁇ 113>.
- step (b) the internals ⁇ 120> in the central chamber K M ⁇ 103> result in turbulence and turbulence in the electrolyte L 3 ⁇ 114> flowing through the central chamber K M ⁇ 103> during the method according to the invention .
- This slows down or completely prevents the build-up of a pH gradient during the electrolysis, which protects the acid-sensitive solid electrolyte FK ⁇ 111> and thus enables the electrolysis to run longer or prolongs the life of the electrolysis cell.
- step (c) a voltage is then applied between EA ⁇ 104> and EK ⁇ 105>.
- the charge source is known to those skilled in the art and is typically a rectifier that converts alternating current into direct current and can generate certain voltages via voltage converters.
- This in turn has the following consequences: the solution L 1 ⁇ 115> is obtained at the outlet A KK ⁇ 109>, with the concentration of XOR in L 1 ⁇ 115> being higher than in L 2 ⁇ 113>, at outlet A KA ⁇ 106> an aqueous solution L 4 ⁇ 116> of S is obtained, the concentration of S in L 4 ⁇ 116> being lower than in L 3 ⁇ 114>.
- the area of the solid electrolyte that contacts the anolyte located in the middle chamber K M ⁇ 103> is in particular 0.00001 to 10 m 2 , preferably 0.0001 to 2.5 m 2 , more preferably 0.0002 to 0.15 m 2 , even more preferably 2.83 cm 2 . It goes without saying that step (c) of the method according to the second aspect of the invention is carried out when both chambers K M ⁇ 103> and K A ⁇ 101> are at least partially loaded with L 3 ⁇ 114> and K K ⁇ 102> is at least partially loaded with L2 ⁇ 113>.
- step (c) charge transport takes place between E A ⁇ 104> and E K ⁇ 105> implies that K K ⁇ 102>, K M ⁇ 103> and K A ⁇ 101> simultaneously with L 2 ⁇ 113> or L 3 ⁇ 114> are loaded in such a way that they cover the electrodes EA ⁇ 104> and EK ⁇ 105> to such an extent that the current circuit is closed.
- step (a) and step (b) are carried out continuously and voltage is applied in accordance with step (c).
- step (c) After step (c) has been carried out, solution L 1 ⁇ 115> is obtained at outlet A KK ⁇ 109>, the concentration of XOR in L 1 ⁇ 115> being higher than in L 2 ⁇ 113>.
- the concentration of XOR in L 1 ⁇ 115> is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, still more preferably 1.077 to 1.4 fold more preferably 1077 to 1.08 times higher than in L2 ⁇ 113>, most preferably 1077 times higher than in L 2 ⁇ 113>, more preferably the mass fraction of XOR in L 1 ⁇ 115> and in L 2 ⁇ 113> is in the range of 10 to 20% by weight, more preferably 13 to 14% by weight.
- an aqueous solution L 4 ⁇ 116> of S is obtained, the concentration of S in L 4 ⁇ 116> being lower than that in L 3 ⁇ 114>.
- the concentration of the cation X in the aqueous solution L 3 ⁇ 114> is preferably in the range of 3.5 to 5 mol/l, more preferably 4 mol/l.
- the concentration of the cation X in the aqueous solution L 4 ⁇ 116> is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 ⁇ 114> used in each case.
- the method according to the second aspect of the invention is carried out at a temperature of 20°C to 70°C, preferably 35°C to 65°C, more preferably 35°C to 60°C, even more preferably 35°C to 50°C and a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, more preferably 1.0 bar.
- hydrogen is typically produced in the cathode chamber K K ⁇ 102>, which hydrogen can be discharged from the cell together with the solution L 1 ⁇ 115> via the outlet A KK ⁇ 109>.
- the mixture of hydrogen and solution L 1 ⁇ 115> can then be separated by methods known to those skilled in the art.
- the alkali metal compound used is a halide, in particular chloride, chlorine or another halogen gas can be produced, which can escape from the cell via the outlet A KK ⁇ 106> together with the solution L 4 ⁇ 116> can be discharged.
- oxygen and/or carbon dioxide can also be formed, which can also be removed.
- the mixture of chlorine, oxygen and/or CO2 and solution L 4 ⁇ 116> can then be separated by methods known to those skilled in the art.
- the gases chlorine, oxygen and/or CO 2 have been separated from the solution L 4 ⁇ 116>, these can be separated from one another by methods known to those skilled in the art.
- the method according to the invention is therefore more efficient than the procedure described in WO 2008/076327 A1, in which the product solution is used for the middle chamber, which reduces the overall turnover.
- the acid-labile solid electrolyte is stabilized by preventing the formation of a pH gradient due to the built-in components ⁇ 120>.
- NM Sodium methoxide
- the electrolytic cell consisted of three chambers, which corresponded to those shown in Figure 1, except that the electrolytic cell had no installations in the middle chamber, ie it did not include the wire basket ⁇ 122> with the glass balls ⁇ 121> shown in Figure 1.
- the connection between the middle and anode chamber was made by a hose that was attached to the bottom of the electrolytic cell.
- the anode compartment and middle compartment were separated by a 2.83 cm2 anion exchange membrane (Tokuyama AMX, ammonium groups on polymer).
- the cathode and middle chamber were separated by a NaSICON type ceramic with an area of 2.83 cm2.
- the ceramic had a chemical composition of the formula Na3.4Zr2.0Si2.4P0.6O12.
- the anolyte was transferred to the anode compartment through the middle compartment.
- the flow rate of the anolyte was 1 l/h, that of the catholyte was 90 ml/h and a current of 0.14 A was applied.
- the temperature was 35°C.
- the electrolysis was carried out for 500 hours with the voltage remaining constant at 5V.
- Comparative example 2 Comparative example 1 was repeated with a two-chamber cell comprising only an anode and a cathode chamber, the anode chamber being separated from the cathode chamber by the ceramic of the NaSICON type. Thus, this electrolytic cell did not contain a center chamber.
- This gradient can make electrolysis even more difficult, especially in the case of very long running times, and can lead to corrosion and ultimately fracture of the solid electrolyte.
- this pH gradient is destroyed, which, in addition to the stated advantages that a three-chamber cell has over a two-chamber cell, further increases the stability of the solid electrolyte.
Abstract
Description
Claims
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KR1020237045183A KR20240023533A (en) | 2021-06-29 | 2022-06-22 | Three-chamber electrolytic cell for the production of alkali metal alkoxides |
CN202280046253.5A CN117580977A (en) | 2021-06-29 | 2022-06-22 | Three-compartment electrolytic cell for producing alkali metal alkoxides |
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EP21182470.1 | 2021-06-29 | ||
EP21182470.1A EP4112780B1 (en) | 2021-06-29 | 2021-06-29 | Three-chamber electrolysis cell for the production of alkali metal alcoholate |
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WO2023274796A1 true WO2023274796A1 (en) | 2023-01-05 |
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PCT/EP2022/066943 WO2023274796A1 (en) | 2021-06-29 | 2022-06-22 | Three-chamber electrolytic cell for the production of alkali metal alkoxides |
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EP (1) | EP4112780B1 (en) |
KR (1) | KR20240023533A (en) |
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EP4112780B1 (en) | 2023-08-02 |
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